CN112724585A - ABS modified material with low butadiene residual quantity and preparation method thereof - Google Patents
ABS modified material with low butadiene residual quantity and preparation method thereof Download PDFInfo
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- CN112724585A CN112724585A CN202011203603.3A CN202011203603A CN112724585A CN 112724585 A CN112724585 A CN 112724585A CN 202011203603 A CN202011203603 A CN 202011203603A CN 112724585 A CN112724585 A CN 112724585A
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 85
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003607 modifier Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001993 dienes Chemical class 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 43
- 238000001125 extrusion Methods 0.000 claims description 24
- 238000005469 granulation Methods 0.000 claims description 24
- 230000003179 granulation Effects 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000006757 chemical reactions by type Methods 0.000 claims description 22
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 14
- 229920002223 polystyrene Polymers 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 6
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- -1 phenyl-maleimide-maleic anhydride-styrene-acrylonitrile Chemical compound 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 150000001923 cyclic compounds Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- UNOSTTDASQMGGW-UHFFFAOYSA-N furan-2,5-dione 5-phenylpenta-2,4-dienenitrile 1-phenylpyrrole-2,5-dione Chemical compound C1(C=C/C(=O)O1)=O.C1(=CC=CC=C1)N1C(C=CC1=O)=O.C(=CC1=CC=CC=C1)C=CC#N UNOSTTDASQMGGW-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MAYCNCJAIFGQIH-UHFFFAOYSA-N buta-1,3-diene 5-phenylpenta-2,4-dienenitrile Chemical compound C=CC=C.N#CC=CC=CC1=CC=CC=C1 MAYCNCJAIFGQIH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 241001061260 Emmelichthys struhsakeri Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an ABS modified material with low butadiene residual quantity and a preparation method thereof, wherein the ABS modified material comprises the following components in parts by weight: ABS resin: 75-97.4 parts; 2-20 parts of a heat-resistant agent: diene reactive modifier: 0.5-4 parts; antioxidant: 0.1 to 1 portion. The diene reactive modifier is prepared by compounding a copolymer with a maleimide-containing side group and active carbon. According to the invention, the double bond in the copolymer with the maleimide-containing side group and the butadiene can interact to generate a cyclic compound, and the 'chance' of the contact between the double bond of the maleimide and the butadiene in the copolymer can be increased by virtue of the higher specific surface area of the activated carbon, so that the residual amount of the butadiene in the ABS modified material is further effectively reduced, the odor of the material is improved, and the requirements of odor and residual amount of the butadiene in various high-end automobile host factories are met.
Description
Technical Field
The invention relates to the field of high-molecular modified materials, in particular to an ABS modified material with low butadiene residual quantity and a preparation method thereof.
Background
ABS resin is a general-purpose thermoplastic engineering plastic, which is composed of three monomers of acrylonitrile, butadiene and styrene, so that the ABS resin keeps the luster and the processing fluidity of Polystyrene (PS) and has excellent impact toughness, and the acrylonitrile increases the rigidity and the strength and has very excellent comprehensive performance. Therefore, the method is widely applied to the fields of automobiles, electronics, office equipment and the like. With the rapid development of the automobile industry in recent years, plastics are widely applied in the automobile field, and particularly, the plastics proposed nowadays are used for replacing steel, and are widely applied to automobile interior parts, such as automobile air conditioner doorways, columns, interior door panels, door handles and the like, due to various excellent characteristics of the ABS resin. However, as the safety, beauty and comfort of the automobile are emphasized by consumers, the high environmental protection performance of the automobile is emphasized, and particularly, the quality of air in the automobile is concerned and emphasized by the consumers and automobile manufacturers. Therefore, the low odor emission of the interior ABS material of the automobile is becoming a trend. The emission and odor of ABS material which is important as interior trim parts of automobiles mainly come from the following aspects: monomer micromolecules and ABS material modification processing aids remained in the early synthesis stage of raw materials of all components, and the ABS component is heated to melt and decomposed under the action of high shear of a screw. Among these, the polybutadiene in the ABS component decomposes into butadiene species upon thermal shearing, which is among a class of carcinogens. Therefore, some high-end automobile host factories such as Benz, Baoma, and land Rover have clear index requirements on the residual amount of butadiene in styrene materials such as ABS and PC/ABS alloy materials.
At present, in order to improve the problem of smell in a vehicle and improve the comfort level, a fragrance agent is mostly added to cover and hide, although the unpleasant smell of plastic is reduced or changed into a relatively acceptable smell, the smell problem is not fundamentally solved. There are also methods of adding a small molecule deodorant, which usually contains water, and although it improves the odor of the material, it is liable to hydrolyze the polymer resin material, seriously affecting the properties of the material, and then affecting the normal use of the product. In addition, no report is found on the reduction of the residual amount of butadiene in ABS materials. Therefore, an ABS modified material with low butadiene residual quantity and without losing material performance is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an ABS modified material with excellent performance and low butadiene residual quantity and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
an ABS modified material with low butadiene residue comprises the following components in parts by weight:
ABS resin: 75-97.4 parts;
heat-resistant agent: 2-20 parts of a solvent;
diene reactive modifier: 0.5-4 parts;
antioxidant: 0.1 to 1 portion.
The molecular weight of the ABS resin is 100000-200000, and the melt index is 5-30 g/10 min.
The heat-resistant agent is any one or more than two of maleic anhydride-styrene copolymer, N phenyl-maleimide-maleic anhydride-styrene copolymer and N phenyl-maleimide-maleic anhydride-styrene-acrylonitrile copolymer.
The diene reactive modifier is prepared by compounding a copolymer with a maleimide-containing side group and active carbon. Wherein the mass ratio of the copolymer with the maleimide-containing side group to the active carbon is 5-20: 1.
The copolymer with the maleimide-containing side group is any one or the combination of more than two of polystyrene with the maleimide-containing side group, styrene-acrylonitrile copolymer with the maleimide-containing side group and styrene-acrylonitrile-butadiene copolymer with the maleimide-containing side group.
The aperture of the activated carbon is 50-100 nm.
The antioxidant is a hindered classified antioxidant or phosphite antioxidant, and comprises any one or a combination of more than two of a commercially available antioxidant 1010, an antioxidant 1076, an antioxidant 1098, an antioxidant 168 and an antioxidant 618.
The preparation method of the ABS modified material with low butadiene residue comprises the following steps:
(1) preparation of diene reactive modifier
Dissolving the copolymer with the maleimide-containing side group and the activated carbon in an excessive acetone solution according to a certain weight ratio, carrying out ultrasonic dissolution at 50-70 ℃, fully soaking for 4-10 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding ABS resin, a heat-resistant agent, a diene reactive modifier and an antioxidant into a mixer for premixing, and controlling the rotating speed of the mixer to be 100-300 r/min and the mixing time to be 5-20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, the screw rotating speed to be 300-600 r/min and the vacuum degree to be-0.06-0.08 MPa, and carrying out granulation to prepare the ABS modified material with low butadiene residue.
Compared with the prior art, the invention has the following beneficial effects:
the diene reaction type modifier is prepared by a method of compounding a copolymer with a maleimide-containing side group and active carbon, wherein the copolymer with the maleimide-containing side group is attached to the inner surface and the outer surface of the active carbon. On one hand, the surface of the activated carbon has the copolymer, so that the activated carbon has good dispersibility in the ABS modified material, and simultaneously, the heat resistance of the ABS modified material can be properly improved due to the existence of the maleimide. In addition, due to the excellent adsorption effect of the activated carbon, organic small molecules such as benzene, toluene, styrene, butadiene and the like in the ABS modified material can be adsorbed, so that the odor of the material and the residual amount of butadiene are reduced. On the basis, double bonds in the copolymer with the maleimide on the side group can interact with butadiene to generate a cyclic compound, and the 'opportunity' of the double bonds of the maleimide in the copolymer to contact with the butadiene can be increased by means of the higher specific surface area of the activated carbon, so that the residual amount of the butadiene in the ABS modified material is further effectively reduced, the smell of the material is improved, and the requirements of the smell and the residual amount of the butadiene in various high-end automobile host factories are met.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Comparative example 1
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
adding 90 parts of ABS resin (the melt index is 15g/10min), 9 parts of maleic anhydride-styrene copolymer, 10100.5 parts of antioxidant and 1680.5 part of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixing stirrer to be 100r/min, and mixing for 5 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 300r/min and the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the ABS modified material.
Comparative example 2
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
(1) preparation of diene reactive modifier
Mixing polystyrene with maleimide-containing side group and activated carbon (with the aperture of 50nm) according to the weight ratio of 2: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 60 ℃, soaking for 4 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding 88 parts of ABS resin (the melt index is 15g/10min), 9 parts of maleic anhydride-styrene copolymer, 2 parts of diene reaction type modifier, 10100.5 parts of antioxidant and 1680.5 part of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 100r/min, and mixing for 5 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 300r/min and the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the ABS modified material.
Comparative example 3
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
(1) preparation of diene reactive modifier
Mixing polystyrene with maleimide-containing side group and active carbon (aperture 100nm) according to the weight ratio of 25: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 55 ℃, soaking for 4 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding 88 parts of ABS resin (the melt index is 15g/10min), 9 parts of maleic anhydride-styrene copolymer, 2 parts of diene reaction type modifier, 10100.5 parts of antioxidant and 1680.5 part of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 100r/min, and mixing for 5 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 300r/min and the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the ABS modified material.
Example 1
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
(1) preparation of diene reactive modifier
Mixing polystyrene with maleimide-containing side group and activated carbon (with the aperture of 50nm) according to the weight ratio of 5: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 50 ℃, soaking for 4 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding 88 parts of ABS resin (the melt index is 15g/10min), 9 parts of maleic anhydride-styrene copolymer, 2 parts of diene reaction type modifier, 10100.5 parts of antioxidant and 1680.5 part of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 100r/min, and mixing for 5 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 300r/min and the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the ABS modified material.
Example 2
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
(1) preparation of diene reactive modifier
Mixing a styrene-acrylonitrile copolymer with a maleimide-containing side group and activated carbon (with the aperture of 100nm) according to a weight ratio of 20: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 70 ℃, soaking for 10 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding 93.5 parts of ABS resin (the melt index is 15g/10min), 2 parts of N-phenyl-maleimide-maleic anhydride-styrene copolymer, 4 parts of diene reaction type modifier, 10100.1 parts of antioxidant and 1680.4 parts of antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixer to be 300r/min and the mixing time to be 20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, the screw rotating speed to be 600r/min and the vacuum degree to be-0.08 MPa, and carrying out granulation to obtain the ABS modified material.
Example 3
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
(1) preparation of diene reactive modifier
Mixing styrene-acrylonitrile-butadiene with a maleimide-containing side group and activated carbon (with the aperture of 80nm) according to the weight ratio of 10: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 70 ℃, soaking for 8 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding 79 parts of ABS resin (the melt index is 5g/10min), 20 parts of N-phenyl-maleimide-maleic anhydride-styrene-acrylonitrile copolymer, 0.5 part of diene reaction type modifier, 10100.3 parts of antioxidant and 1680.2 parts of antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixer to be 250r/min and the mixing time to be 20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, the screw rotating speed to be 400r/min and the vacuum degree to be-0.08 MPa, and carrying out granulation to obtain the ABS modified material.
Example 4
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
(1) preparation of diene reactive modifier
Mixing styrene-acrylonitrile-butadiene containing maleimide on a side group, polystyrene containing maleimide on a side group (the mass ratio of the styrene-acrylonitrile-butadiene containing maleimide on the side group to the polystyrene containing maleimide on the side group is 1:1) and active carbon (with the aperture of 50nm) according to the weight ratio of 12: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 60 ℃, soaking for 9 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding 97.4 parts of ABS resin (the melt index is 30g/10min), 2 parts of N-phenyl-maleimide-maleic anhydride-styrene-acrylonitrile copolymer, 0.5 part of diene reaction type modifier, 10100.1 parts of antioxidant and 1680.1 parts of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 250r/min, and mixing for 20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, the screw rotating speed to be 400r/min and the vacuum degree to be-0.08 MPa, and carrying out granulation to obtain the ABS modified material.
Example 5
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
(1) preparation of diene reactive modifier
Mixing a styrene-acrylonitrile copolymer with a side group containing maleimide, polystyrene with a side group containing maleimide (the mass ratio of the styrene-acrylonitrile copolymer with the side group containing maleimide to the polystyrene with the side group containing maleimide is 2:1) and activated carbon (with a pore diameter of 75nm) according to a weight ratio of 15: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 65 ℃, soaking for 10 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding 82.4 parts of ABS resin (the melt index is 20g/10min), 15 parts of N-phenyl-maleimide-maleic anhydride-styrene-acrylonitrile copolymer, 2 parts of diene reaction type modifier, 10100.2 parts of antioxidant and 1680.4 parts of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 250r/min, and mixing for 20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 450r/min and controlling the vacuum degree to be-0.08 MPa, and carrying out granulation to obtain the ABS modified material.
Example 6
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
(1) preparation of diene reactive modifier
Mixing a styrene-acrylonitrile copolymer with a side group containing maleimide, polystyrene with a side group containing maleimide (the mass ratio of the styrene-acrylonitrile copolymer with the side group containing maleimide to the polystyrene with the side group containing maleimide is 2:1) and activated carbon (with a pore diameter of 100nm) according to a weight ratio of 8: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 55 ℃, soaking for 7 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding 85 parts of ABS resin (the melt index is 20g/10min), 5 parts of N-phenyl-maleimide-maleic anhydride-styrene copolymer, 5 parts of N-phenyl-maleimide-maleic anhydride-styrene-acrylonitrile copolymer, 4 parts of diene reaction type modifier, 10100.4 parts of antioxidant and 1680.6 parts of antioxidant into a mixing stirrer for premixing, and controlling the rotating speed of the mixer to be 150r/min and the mixing time to be 15 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 500r/min and controlling the vacuum degree to be-0.07 MPa, and carrying out granulation to obtain the ABS modified material.
Example 7
An ABS modified material with low butadiene residual quantity and a preparation method thereof, comprising the following steps:
(1) preparation of diene reactive modifier
The method comprises the following steps of (1) taking a copolymer with a maleimide-containing side group as a polystyrene with a maleimide-containing side group, a styrene-acrylonitrile copolymer with a maleimide-containing side group, a styrene-acrylonitrile-butadiene copolymer with a maleimide-containing side group (the copolymer with a maleimide-containing side group is a polystyrene with a maleimide-containing side group, the styrene-acrylonitrile-butadiene copolymer with a maleimide-containing side group is prepared, and the mass ratio of the styrene-acrylonitrile-butadiene copolymer with a maleimide-containing side group to active carbon (the aperture is 80nm) in a weight ratio of 16: dissolving 1 in excessive acetone solution, carrying out ultrasonic dissolution at 65 ℃, soaking for 5 hours, filtering, and drying to obtain the diene reaction type modifier for later use.
(2) Preparation of ABS modified Material
Adding 75 parts of ABS resin (the melt index is 20g/10min), 5 parts of maleic anhydride-styrene copolymer, 10 parts of N-phenyl-maleimide-maleic anhydride-styrene copolymer, 5 parts of N-phenyl-maleimide-maleic anhydride-styrene-acrylonitrile copolymer, 4 parts of diene reaction type modifier, 10100.5 parts of antioxidant and 1680.5 part of antioxidant into a mixing stirrer for premixing, controlling the rotating speed of the mixer to be 200r/min, and mixing for 10 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, controlling the screw rotation speed to be 550r/min and controlling the vacuum degree to be-0.06 MPa, and carrying out granulation to obtain the ABS modified material.
According to the ABS modified material prepared in the comparison column 1 and the examples 1-7, test sample strips are prepared according to the same injection molding process conditions, and the specific evaluation methods of mechanical properties, odor and butadiene residual quantity are as follows:
tensile strength: testing according to ISO527 standard;
flexural strength and modulus: testing according to ISO178 standard;
vicat softening temperature: testing according to ISO306 standard;
notched impact strength (23 ℃ and-30 ℃): testing according to ISO179-1 standard;
odor characteristics were tested according to VDA270 standard (20 g);
the butadiene residual was tested in accordance with DIN EN 13130.
As can be seen from the above table, the odor of the ABS modified material can be obviously improved by adding a certain amount of the reactive modifier, and the residual amount of butadiene can be reduced. As in example 2, 4 parts of odor eliminating agent was added, the odor grade was 3, and the residual butadiene content was 0.4 ug/g. The ABS modified material with low butadiene residue prepared by the invention can meet the requirements of high-end vehicles such as gallop and BMW on the emission performance of automobile materials, and has wide application prospect.
Claims (9)
1. An ABS modified material with low residual butadiene content is characterized in that: the paint comprises the following components in parts by weight:
ABS resin: 75-97.4 parts;
heat-resistant agent: 2-20 parts of a solvent;
diene reactive modifier: 0.5-4 parts;
antioxidant: 0.1 to 1 portion.
2. The ABS modified material with low residual butadiene content as claimed in claim 1, wherein: the molecular weight of the ABS resin is 100000-200000, and the melt index is 5-30 g/10 min.
3. The ABS modified material with low residual butadiene content as claimed in claim 1, wherein: the heat-resistant agent is any one or more than two of maleic anhydride-styrene copolymer, N phenyl-maleimide-maleic anhydride-styrene copolymer and N phenyl-maleimide-maleic anhydride-styrene-acrylonitrile copolymer.
4. The ABS modified material with low residual butadiene content as claimed in claim 1, wherein: the diene reaction type modifier is prepared by compounding a copolymer with a maleimide-containing side group and active carbon, wherein the mass ratio of the copolymer with the maleimide-containing side group to the active carbon is 5-20: 1.
5. The ABS modified material with low residual butadiene content as claimed in claim 4, wherein: the copolymer with the maleimide-containing side group is any one or the combination of more than two of polystyrene with the maleimide-containing side group, styrene-acrylonitrile copolymer with the maleimide-containing side group and styrene-acrylonitrile-butadiene copolymer with the maleimide-containing side group.
6. The ABS modified material with low residual butadiene content as claimed in claim 4, wherein: the aperture of the activated carbon is 50-100 nm.
7. The ABS modified material with low residual butadiene content as claimed in claim 1, wherein: the antioxidant is a hindered classified antioxidant or a phosphite antioxidant.
8. The ABS modified material with low residual butadiene content as claimed in claim 7, wherein: the antioxidant is any one or combination of more than two of a commercially available antioxidant 1010, an antioxidant 1076, an antioxidant 1098, an antioxidant 168 and an antioxidant 618.
9. The process for preparing an ABS modified material with a low residual butadiene content according to any of claims 1 to 8, wherein the process comprises the steps of: the method comprises the following steps:
(1) preparation of diene reactive modifier
Dissolving a copolymer with a maleimide-containing side group and activated carbon in an excessive acetone solution according to a certain weight ratio, performing ultrasonic dissolution at 50-70 ℃, fully soaking for 4-10 hours, filtering, and drying to obtain a diene reaction type modifier for later use;
(2) preparation of ABS modified Material
Adding ABS resin, a heat-resistant agent, a diene reactive modifier and an antioxidant into a mixer for premixing, and controlling the rotating speed of the mixer to be 100-300 r/min and the mixing time to be 5-20 min; and then carrying out melt blending extrusion granulation on the obtained mixture by a double-screw extruder, controlling the extrusion temperature to be 230-270 ℃, the screw rotating speed to be 300-600 r/min and the vacuum degree to be-0.06-0.08 MPa, and carrying out granulation to prepare the ABS modified material with low butadiene residue.
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Cited By (2)
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| CN116554409A (en) * | 2023-05-10 | 2023-08-08 | 金发科技股份有限公司 | Modified ABS rubber powder, preparation method thereof, ABS resin and vehicle interior trim part |
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